Phase Stability Of Alloys Research Articles

Phase Behavior and Atomic Dynamics in RbxNa1-x: Insights from Machine Learning Interatomic Potentials based on Ab Initio Molecular Dynamics.

Liquid alkali metal alloys have garnered significant attention because of their potential applications in coolant systems and batteries, driven by the need for environmental conservation and technological development. However, research on these complex systems is limited, necessitating a deeper understanding to ensure their safe and effective utilization. This study presents a comprehensive investigation of the factors that determine the phase diagram of RbxNa1-x. By reproducing the experimental results using the thermodynamic integration method and machine learning interatomic potentials based on ab initio molecular dynamics simulations, we uncovered the delicate balance between the energy and entropy contributions that influence the phase stability of these liquid metal alloys. Further analysis of the liquid phase revealed the crucial roles of volume and atomic mass. Additionally, the coordination numbers of the atoms revealed distinct clustering behaviors, where Na atoms tended to avoid proximity to other Na atoms, whereas Rb atoms exhibited a strong tendency to cluster together. Moreover, the diffusion dynamics further illustrated the asymmetry in the behavior of Rb and Na, with Rb showing increased diffusion at higher concentrations and Na exhibiting higher diffusion at lower concentrations. These findings offer significant insights into the phase stability and the dynamic and structural properties of these complex liquid metal alloys.

Role of Anharmonic Effects on the Phase Stability of VNbMoTaW High-Entropy Alloy from Ab Initio Analysis

Role of Anharmonic Effects on the Phase Stability of VNbMoTaW High-Entropy Alloy from Ab Initio Analysis

Influence of β-Stabilizing Nb on Phase Stability and Phase Transformation in Ti-Zr Shape Memory Alloys: From the Viewpoint of the First-Principles Calculation

In the present study, the effect of the Nb element on the lattice parameters, phase stability and martensitic transformation behaviors of Ti-Zr-based shape memory alloys was extensively investigated using the first-principles calculation. The lattice parameters of both the β parent phase and α′ martensite phase gradually decreased with Nb content increasing. For the α″ martensite phase, the lattice constant (a) gradually increased with the increase in Nb content, whereas the lattice constants (b and c) continuously decreased due to the addition of Nb. Based on the formation energy and density of state, β→α′ martensitic transformation occurred, as the Nb content was not more than 12.5 at.%. However, the Ti-Zr-Nb shape memory alloys with a Nb content higher than 12.5 at.% possessed the β→α″ martensitic transformation. However, both the largest transformation strain and sensitivity of critical stress to temperature (dσ/dT) can be optimized by controlling 12.5 at.% Nb in the Ti-Zr-Nb shape memory alloy, which was favorable to obtaining the largest elastocaloric effect.

Effect of Cu Alloying and Heat Treatment Parameters on NiTi Alloy Phase Stability and Constitutive Behavior

Effect of Cu Alloying and Heat Treatment Parameters on NiTi Alloy Phase Stability and Constitutive Behavior

Antiferromagnetism and Phase Stability of CrMnFeCoNi High-Entropy Alloy.

It has long been suspected that magnetism could play a vital role in the phase stability of multicomponent high-entropy alloys. However, the nature of the magnetic order, if any, has remained elusive. Here, by using elastic and inelastic neutron scattering, we demonstrate evidence of antiferromagnetic order below ∼80 K and strong spin fluctuations persisting to room temperature in a single-phase face-centered cubic (fcc) CrMnFeCoNi high-entropy alloy. Despite the chemical complexity, the magnetic structure in CrMnFeCoNi can be described as γ-Mn-like, with the magnetic moments confined in alternating (001) planes and pointing toward the ⟨111⟩ direction. Combined with first-principles calculation results, it is shown that the antiferromagnetic order and spin fluctuations help stabilized the fcc phase in CrMnFeCoNi high-entropy alloy.

First-principles calculations to investigate phase stability, elastic and thermodynamic properties of TiMoNbX (X=Cr, Ta, Cr and Ta) refractory high entropy alloys

This work uses first-principles calculations to investigate the phase stability, thermophysical and mechanical properties of refractory high entropy alloys (RHEAs) at finite temperatures. On the basis of plane wave quasi-potential and density functional theory, construct the structure model of a solid solution. The TiMoNbX (X = Cr, Ta, Cr and Ta) RHEAs have been determined to preserve a single body-centered cubic solid solution structure by calculations and the equilibrium lattice parameters and elastic modulus are consistent with experimental data obtained by laser cladding, which is combined with TC4 (Ti-6Al-4V) substrate. Using the quasi-harmonic Debye-Grüneisen model, the thermophysical characteristics of three RHEAs are investigated. The Voigt-Reuss-Hill scheme is used for calculating the Young's modulus (E), bulk modulus (B), shear modulus (G), and Poisson's ratio (ν), which indicates that all three RHEAs are ductile materials. Additionally, the modulus and hardness of materials decrease as temperature rises, whereas the properties of TiMoNbX RHEAs are predicted, as the nanoindentation hardness values at room temperature are comparable to, and slightly higher than the calculated values.

High Milling Time Influence on the Phase Stability and Electrical Properties of Fe50Mn35Sn15 Heusler Alloy Obtained by Mechanical Alloying.

Fe50Mn35Sn15 Heusler alloy, obtained by mechanical alloying, was subjected to larger milling times in the range of 30-50 h to study the phase stability and morphology. X-ray diffraction studies have shown that the milled samples crystallise in a disordered A2 structure. The A2 structure was found to be stable in the milling range studied, contrary to the computation studies performed on this composition. Using Rietveld refinements, the lattice parameter, mean crystallite size, and lattice strain were computed. The nature of the obtained phases by milling was found to be nanocrystalline with values below 50 nm. A linear increase rate of 0.00713 (h-1) was computed for lattice strain as the milling time increased. As the milling time increases, the lattice parameter of the cubic Heusler was found to have a decreasing behaviour, reaching 2.9517 Å at 50 h of milling. The morphological and elemental distribution-characterised by scanning electron microscopy and energy-dispersive X-ray spectroscopy-evidenced Mn and Sn phase clustering. As the milling time increased, the morphology of the sample was found to change. The Mn and Sn cluster size was quantified by elemental line profile. Electrical resistivity evolution with milling time was analysed, showing a peak for 40 h of milling time.

Phase stability of precipitate-hardened CoCrFeNiTi high entropy alloys fabricated via laser-directed energy deposition under high-temperature irradiation

This study investigated the irradiation response of precipitate-hardened CoCrFeNiTi high entropy alloys (HEAs) fabricated by laser-directed energy deposition (LDED). These HEAs were in-situ irradiated with 1 MeV krypton ions (Kr2+) at 400 °C and 600 °C up to 10 displacements per atom (dpa) at the IVEM-Tandem Facility at Argonne National Laboratory. Transmission electron microscopy (TEM) characterized precipitate stability and defect evolution under irradiation. At 400 °C and 10 dpa, precipitates showed high phase stability, while irradiation at 600 °C caused intense dissolution mainly due to its annealing effect. A high density of faulted dislocation loops formed at 400 °C. The annihilation rate of dislocation loops seemed higher at 600 °C. Increasing the dose increased the number and size of voids in the face-centered cubic (FCC) matrix.

A comparative study of predicting high entropy alloy phase fractions with traditional machine learning and deep neural networks

Predicting phase stability in high entropy alloys (HEAs), such as phase fractions as functions of composition and temperature, is essential for understanding alloy properties and screening desirable materials. Traditional methods like CALPHAD are computationally intensive for exploring high-dimensional compositional spaces. To address such a challenge, this study explored and compared the effectiveness of random forests (RF) and deep neural networks (DNN) for accelerating materials discovery by building surrogate models of phase stability prediction. For interpolation scenarios (testing on the same order of system as trained), RF models generally produce smaller errors than DNN models. However, for extrapolation scenarios (training on lower-order systems and testing on higher order systems), DNNs generalize more effectively than traditional ML models. DNN demonstrate the potential to predict topologically relevant phase composition when data were missing, making it a powerful predictive tool in materials discovery frameworks. The study uses a CALPHAD dataset of 480 million data points generated from a custom database, available for further model development and benchmarking. Experiments show that DNN models are data-efficient, achieving similar performance with a fraction of the dataset. This work highlights the potential of DNNs in materials discovery, providing a powerful tool for predicting phase stability in HEAs, particularly within the Cr-Hf-Mo-Nb-Ta-Ti-V-W-Zr composition space.

Designing cobalt-free face-centered cubic high-entropy alloys: A strategy using d-orbital energy level

High-entropy alloys (HEAs) are promising materials for high-temperature structural applications such as nuclear reactors due to their outstanding mechanical properties and thermal stability. Instead of the trial-and-error method, it is efficient to design and prepare single-phase face-centered cubic (FCC) structured HEAs using semi-empirical phase formation rules. However, almost all of phase formation rules were proposed without taking into account the cobalt-free situation. The HEAs containing cobalt are unsuitable for nuclear applications because of the long-term activation of cobalt. Here, six parameters, d-orbital energy level, valance electron concentration, entropy of mixing, enthalpy of mixing, atom size differences, and parameter of the entropy of mixing (Ω) were calculated to determine the solid solution phase, especially the FCC phase formation rules in cobalt-free HEAs. HEAs of 4 components were arc melted to verify the newly developed phase formation rules. The nanomechanical properties of produced HEAs were evaluated using nanoindentation. Among the six parameters, the d-orbital energy level and valance electron concentration are the critical factors that determine the FCC phase stability in cobalt-free alloys. Interestingly, the d-orbital energy level can be alone used as a benchmark for developing mechanical properties.

High-Temperature Oxidation and Phase Stability of AlCrCoFeNi High Entropy Alloy: Insights from In Situ HT-XRD and Thermodynamic Calculations.

The high-temperature oxidation behaviour and phase stability of equi-atomic high entropy AlCrCoFeNi alloy (HEA) were studied using in situ high-temperature X-ray diffraction (HTXRD) combined with ThermoCalc thermodynamic calculation. HTXRD analyses reveal the formation of B2, BCC, Sigma and FCC, phases at different temperatures, with significant phase transitions observed at intermediate temperatures from 600 °C-100 °C. ThermoCalc predicted phase diagram closely matched with in situ HTXRD findings highlighting minor differences in phase transformation temperature. ThermoCalc predictions of oxides provide insights into the formation of stable oxide phases, predominantly spinel-type oxides, at high p(O2), while a lower volume of halite was predicted, and minor increase observed with increasing temperature. The oxidation behaviour was strongly dependent on the environment, with the vacuum condition favouring the formation of a thin, Al2O3 protective layer, while in atmospheric conditions a thick, double-layered oxide scale of Al2O3 and Cr2O3 formed. The formation of oxide scale was determined by selective oxidation of Al and Cr, as further confirmed by EDX analysis. The formation of thick oxide in air environment resulted in a thick layer of Al-depleted FFC phase. This comprehensive study explains the high-temperature phase stability and time-temperature-dependent oxidation mechanisms of AlCrCoFeNi HEA. The interplay between surface phase transformation beneath oxide scale and oxides is also detailed herein, contributing to further development and optimisation of HEA for high temperature applications.

Critical impacts of thermodynamic instability and short-range order on deformation mechanisms of VCoNi medium-entropy alloy

Short-range order (SRO) has made a splash in the recent research on multi-principal element alloys (MPEAs), among which the equiatomic VCoNi alloy was regarded as the most potential prototype. However, in addition to disputes over SRO, there is still a lack of agreements on the phase stability and deformation mechanism of the VCoNi alloy, which should be addressed before the SRO can be independently analyzed. To this end, microstructural evolutions with increasing long-term annealing temperatures (from 700 to 1,200 °C) were first inspected in detail to determine critical temperatures for phase transitions unambiguously. Our results revealed that the VCoNi alloy was still dominated by the face-centered-cubic (FCC) structure with a minor κ phase at 900 °C and became a single FCC solid solution at above 910 °C. Subsequently, by carefully examining dislocation configurations and stacking fault (SF) widths in the FCC phases annealed at 900 °C and 1,200 °C, significant variations in local stacking fault energy (SFE) were unveiled, and the overall SFE decreased with increasing annealing temperature. Combined with the state-of-the-art density function theory (DFT)-based lattice Monte Carlo (MC) simulation, we demonstrated how the rise/decline in SFE can be explained by the greater/lower degree of SRO. This research would not only offer new perspectives for recent controversies over phase stability, deformation mechanism, and SRO characterization technique using electron diffraction but also shed light on the intrinsic relationship between SRO and local stacking fault energy of MPEAs.

Computational thermodynamics-guided alloy design and phase stability in CoCrFeMnNi-based medium-and high-entropy alloys: An experimental-theoretical study

A computational thermodynamics approach has been employed to design CoCrFeMnNi-based medium- and high-entropy alloys (M/HEAs) with systematically varied compositions (Co((80-X)/2)Cr((80-X)/2)FeXMn10Ni10 with x = 30, 40, and 50 at.%) and phase stability. Since the formation of sigma phase, usually brittle and undesirable, is a common concern, when this class of alloys is subjected to elevated temperatures (600–1000 °C), predicting its formation becomes essential. Thus, its formation and the phase equilibria were studied using the CALPHAD method, and two empirical methods, namely, valence electron concentration (VEC) and paired sigma-forming element (PSFE). Isothermal aging treatments at 900–1100 °C for 20 h were performed, since CALPHAD and VEC/PSFE predictions diverged. Both prediction methods were compared with experimental characterization by a combination of scanning electron microscopy and high-energy synchrotron X-ray diffraction. The predictions from the VEC/PSFE and CALPHAD calculations (depending on the database used) were shown to be quite accurate.

Phase stability and transition of CrTaVW high-entropy alloy

Refractory high-entropy alloys (RHEAs) are susceptible to phase transition at elevated temperatures, inducing deviation in the phase constitution from the intended design hence affecting the performance significantly. Accurate prediction of phase constitution and modulation of phase stability over a broad temperature range is crucial to develop RHEAs with superior properties. In this study, thermodynamic and first-principles calculations were integrated to investigate the temperature-dependent phase constitution in the CrTaVW alloy system. The effect of V and W atoms occupation sites on the stability of TaCr2 Laves phase was evaluated. Both V or W atoms tend to occupy Cr sites in TaCr2, and V exhibits stronger alloying ability than W due to the reduced electronic density at the Fermi level. Moreover, with increasing the doping content, the V and W exhibit opposite influencing trends on the formation and structural stability of TaCr2 Laves phase. The Gibbs free energies of the Laves phase and solid solutions with variable compositions were obtained, enabling predictions for the critical temperatures of the phase transitions. The predicted behaviors of phase transitions were validated by experiments. This study provides guidance for modulating phase constitution and achieving desirable phase stability in RHEAs.

Evolution of microstructure, mechanical properties and phase stability of CoCrFeMnNi high entropy alloys

In the present study, the microstructure and mechanical properties of various CoCrFeMnNi high-entropy alloys were investigated. Analytical studies were conducted to determine the optimal chemical composition, mixing entropy, mixing enthalpy, atomic radii, valence electron concentration (VEC), dimensionless parameter, and melting point on the Co-Cr-Fe-Mn-Ni system. The microstructure of the alloys was analyzed using FESEM, XRD, and TEM. The results showed that the microstructure of all HEAs had dendritic and interdendritic regions, with secondary precipitations detected along the grain boundaries of the alloy, mainly composed of Mn and Ni. High-density dislocation structures and nano-precipitates were predominantly present in the alloy. The mechanical characteristics such as microhardness and tensile properties are conducted at room temperature. The HEA Co25Cr25Fe10Mn30Ni10 exhibited the highest average microhardness, while the Co20Cr20Fe30Mn10Ni20 HEA had the lowest mean hardness value. This significant difference of 7.2 % may be attributed to the hard phases composed of Mn and Ni. The results of the tensile experiments indicate that the Co20Cr20Fe20Mn20Ni20 alloy has the most favorable overall properties, with an ultimate tensile strength of 441 MPa. This represents a significant increase of 37.8 % compared to 20Cr20Fe20Mn20Ni20. Furthermore, the study examines the instability of the solid-solution state caused by differences in the valence electron concentrations of the constituent elements and phase stability.

Atomic-scale investigation of Mo distribution and its effect on phase stability of a nanocrystalline CrCoNi-based medium-entropy alloy

“Suzuki segregation” of Mo to planar defects was proposed to contribute to secondary hardening after post-deformation annealing in the MP35N alloy, a CrCoNi-based single-phase superalloy. However, a direct proof of this proposal is challenging and reported observations are controversial. Here, we prepared nanocrystalline MP35N thin films by co-deposition on a microtip array of pre-sharpened Si tips. This enabled a direct investigation of the Mo distribution in a nanoscale structure with many grain boundaries (GBs) after annealing by atom probe tomography. We observed that no Mo but Cr segregates to GBs between 360 and 460 °C. Additionally, we found that MP35N is thermally more stable than a (Mo-free) Cr-Co-Ni medium-entropy alloy under the same conditions. Factors that influence the kinetics of phase decomposition and thermal stability, including grain size, Mo addition, and the loss of Cr due to oxidation at GBs were addressed.

Understanding the magnetism-ductility trade-off in FeCoMn alloys: The role of the BCC-B2 transition and Mn occupancies

The magnetism-ductility contradictory relationship presents a significant challenge in the development of magnetic alloys. The impact of the BCC-B2 transition, along with Mn site occupancy, on magnetism and ductility have been investigated by using first-principles calculations. The calculations involved the evaluation of magnetic moments, density of states (DOS), phase stability and ductility of FeCoMn alloys. The results of binary alloys confirm the enhancement of magnetism due to the BCC-B2 transition. Furthermore, the ordering phase transition can strengthen the magnetic interaction between Fe and Mn atoms, which is associated with minimal variations in the density of states of Fe and Mn in the B2 structure. Regarding the ductility of FeCoMn alloys, two factors contribute to increased brittleness. Firstly, the increased covalent component in bonding, as a result of the strong hybridization between different elements, leads to an increased brittleness. Secondly, the increased Peierls stress provides a larger resistance to dislocation motion, which also contributes to the increased brittleness. Finally, the Pearson correlation coefficients and data analysis indicate that VEC, spin polarizations and Mn content provide major contributions to the contradictory relationship between magnetism and ductility.

Phase stability and mechanical properties of the six-principal element TiVNbCrCoNi alloys

This study designed a series of six-principal element TiVNbCrCoNi alloys according to the maximum entropy principle under the constraint of valence electron concentration (VEC). The phase stability and mechanical properties were investigated. It was showed that at VEC levels below 5.2, the body-centered cubic (BCC)-structured solid-solution phase remained stable at room temperature. As VEC exceeded 8.0, the face-centered cubic (FCC)-structured solid-solution phase stabilized. In the VEC range of 5.2–8.0, (Co, Ni)Ti and Ni3Nb intermetallic compounds formed combining with the solid-solution phases. Both yield strength and ductility increased with increase of VEC in the BCC-structured solid-solution alloys. The phase stability was elucidated through First-principle and thermodynamic calculations, while the evolution of mechanical properties of solid-solution alloys was evaluated in terms of multiple parameters. The thermodynamic calculation achieved satisfactory accuracy after being adjusted to utilize atomic bond enthalpy instead of atomic electronegativity difference.

Body-centered cubic phase stability in cobalt-free refractory high-entropy alloys

Cobalt-free refractory high-entropy alloys (RHEAs) are strong contenders for structural materials in nuclear reactors because they do not exhibit cobalt activity under irradiation. The mechanical properties and thermal stability of RHEAs are primarily attributed to the solid solution phase, which is essentially the body-centered cubic (BCC) phase. The BCC phase formation rules thus became the basic criterion in the compositional design of RHEAs. In this paper, the BCC phase formation rules in cobalt-free RHEAs were determined via the calculation of six semiempirical parameters, namely, the entropy of mixing, enthalpy of mixing, atomic size difference, Ω-parameter, d-orbital energy level and valance electron concentration. The mixing enthalpy and atomic size differences are more effective than other semiempirical parameters for predicting BCC phase stability in cobalt-free RHEAs. The presence of aluminum is found to cause a notable alteration in the range of phase stability in cobalt-free RHEAs.

Chemomechanics in alloy phase stability

Chemomechanics in alloy phase stability